Polyazo-dyestuffs



United tates PatentO "Ce 2,711,838

Patented Jan. 15, 1957 naphthalene-monoor disulfonic acid coupled in an acid 2,777,333 medium with a diazo-compound and the resulting diazopoLYA a YEs u azo-compound is combined in an alkaline medium with 1 molecular proportion of the azo-dyestutf obtained from Richard Huss Arthur siebert, and Josgf weisSfl-t, Frank 5 a sulfonated diazoor d1azo-azo-compound and 3.3'-d1- furt am Main, Germany, assignors to Farbwerke y yp fly Hoechst Aktiengesellschaft vormals Meister Lucius & The invention also includes a further process for mak- Bnming, Frankfurt am Main, y, a 'lw ing the aforesaid polyazo-dyestuifs, wherein 1 molecular of Germany proportion of the tetrazotized diamino-compound is No Drawing. Application May 21, 1954, coupled in an alkaline medium with 1 molecular propor- Seria] 431,595 men of a 1 amino 8 hydroxynaphthalene monoor disulfonic acid or of a 1 amino 8 hydroxynaph-thalenemonoor disulfonic acid coupled in an acid medium with a diazo-compoond and the diazo-azo-compound so ob- The present invention relates to new polyazo-dyestuffs; tained and 1 molecular proportion of a diazoor diazo- 4 Claims. (Cl. 260-168) more particularly it relates to the polyazo-dyestuffs corazo-cornpound are coupled simultaneously with 1 molecuresponding to the following general formula lar proportion of 3.3'-dihydroxy-diphenylamine.

OH OH H21? (BK Z N=N N=N (N=N-R2) wherein 2 represents hydrogen, the sulfonic acid group The new dyestuffs are readily soluble in water and are or the group N=N-R1, R1 and R2 represent aromatic resistant to inorganic and organic acids as well as to radicals, X stands for the diphenyl bond, -CH=CH-, alkalies and formaldehyde. They havea great affinity for -NHCONH, CO-, O-, S, NH or leather fibres, and dye all kinds of leather by drum dye- CONH-, Y represents hydrogen or the sulfonic acid ing, brush dyeing or spray dyeing, deep full tints which group, and wherein the phenyl radicals a may contain range from violet, dark green through dark blue to black substituents. and possess a good to very good fastness to light.

We have found that new valuable polyazo-dyestuffs The following examples serve to illustrate the invention corresponding to the general constitution but they are not intended to limit it thereto; the parts 3 acid mmimshydmw alkaline being by weight unless otherwise stated, 'and the relationmine -n Hr ship of parts by weight to parts by volume belng the same as that of the kilogram to the liter:

Example 1 Q 40 A diazo-suspension prepared in the usual manner from 173 parts of 1 aminobenzene 4 sulfonic acid is coupled in an acid medium with 341 parts of 1 amino 8- hydroxynaphthalene 3.6 disulfonic acid (monosodium salt) and the coupling is completed by neutralizing the (amine 3.3-dihydroxydi- H N phenylamine are obtained by coupling 1 molecular proportion of a tetrazo-compound of a diamine of the general formula HIEN NHi excess of the acid with a 2 N-solution of sodium acetate.

5 To the suspension of the monoazo-dyestufi so obtained a v tetrazo-solution prepared from 184 parts of 4.4-d.iaminoin which X has the meaning given above, and the two fiiphenylis added i 00 and col'lpling is conducted phenyl radicals may contain substituents, in an alkaline a Weakly alkalme m by addmg 9- Parts by medium with 1 molecular proportion of a 1 amino 8- Q f of a N'solutlon sodlum hydro7lde- Affer hydroxynaphtha1ene mno or di lf i acid or of a stirring the mixture for 30 minutes, the alkal ne solution amino 8 hydroxynaphthalene monoor disulfonic acid 9 201 P dlhydroxy dlPhenylamme addefl coupled in an acid medium with a diazo-compound, comone pomfm and the reactwn-mlxture obtamed. 1s bining the diazo-azo-compound so obtained in an alkaline Ftlrred ovemlght at 3 P value of 9- when the f P or acetic acid medium with 1 molecular proportion of a is complete the 501mm of tnsefzo'dyestufi 15 f 3.3 dihydroxy diphenylamine and, if desired, coupling fled, hfiatfid t0 2 Salted Out Wlth a small q f y the resulting polyazo dyesmff with any diazoor i of sodlum chloride, filtered OE With suction and dried. azo-compound The dyestuff obtained as a grey-black powder is very The invention also includes an alternative process for readily So In Water and feslstal'lt t0 lnorgamc and making polyazo-dyestuffs of the above constitution, whereorganic acids, as well as to formaldehyde and alkalies. in 1 molecular proportion of the tetrazotized diamino- The trisazo-dyestuif so obtained dyes all kinds of leather compound i coupled in an alkaline medium with l molecdeep bluish-black uniform tints having a good covering ular proportion of a 1 amino 8 hydroxynaphthalenepower and very good fastness to light. It corresponds monoor disulfonic acid or of a 1 amino 8 hydroxyto the following formula on no am on I l l NH. Hots 01H,

Example 2 A diam-suspension prepared in the usual manner from 18.7 parts of 1 amino 4 methylbenzene 3 sulfonic acid iscoupled in the usual manner in an acid medium with 34.1 parts of l amino 8 hydroxynaphthalene- 3.6 disulfonic acid (monosodium salt). To the acid suspension of the monoazo-dyestuff so obtained the clarified tetrazo-solution from 18.4 parts of 4.4-diaminodiphenyl is then added and the mixture is combined with the monoazo-compound in a weakly alkaline medium by adding 30 parts of "sodium carbonate. After stirring for 30 minutes, the resulting diazo-disazo-compound is coupled with 20.1 parts of 3.3 dihydroxy diphenylamine, the coupling medium having an alkaline reaction. When the coupling is complete, the trisazo-dyestuff is isolated as described in Example 1. The grey-black powder so obtained dyes various kinds of leather by drum dyeing, brush dyeing and spray dyeing reddish blue-black tints having a good fastness to light and resistance to inorganic and organic acids as well as to alkalies and formaldehyde.

Example 3 The trisazo-dyestulf described in Example 1 and having the constitution: l-aminobenzenel-sulfouic acid acid 1-amino-8-hydroxynaphthalene-3.6-disulf0nic acid alkaline alkaline 4.4-diaminodiphenyl 3.3-dihydroxy-diphenylamine is converted into the tetrakisazodyestufi by coupling it in an alkaline medium at a pH value of with 173 parts of l-aminobenzene-4-sulfonic acid. When the coupling is complete, the dyestuff solution is rendered acid, heated to 92 C, salted out with a small quantity of sodium chloride, filtered off with suction and dried. The tetrakisazo-dyestuff is obtained in the form of a grey-black powder which is very readily soluble in water and has the same good fastness properties as the dyestuff described in Example 1. It dyes all kinds of leather by drum dyeing, brush dyeing and spray dyeing uniform bluish black tints which have, however, a better covering power and avery good fastness to light. The dyestuif corresponds to the following formula HzN (I) H Example 4 A diam-suspension from 207 parts of 1-amino-4- chlorobenzene-3-sulfonic acid is coupled in the usual manner in an acid medium with 341 parts of l-amino-S- hydroxynaphthalene-4.fi-disulfonic acid (monosodium salt) and the monoazo-dyestutf so obtained is then coupled in a weakly alkaline medium with a tetrazo-solution prepared from 184 parts of 4.4'-diaminodiphenyl, while adding 2000 parts by volume of a 2 N-solution of sodium hydroxide. After 30 minutes the resulting diazodisazo-compound is coupled to form the trisazodyestuif by adding an alkaline solution of 201 parts of 3.3-dihydroxydiphenylarnine. The coupling solution is stirred overnight and a tetrakisazo-dyestufi is then obtained by simultaneously adding to the trisazo-dyestuif a diazo-suspension prepared from 207 parts of 1-amino-4-chlorobeuzene-3-sulfonic acid and 200 parts by volume of a 5 N-solution of sodium hydroxide. The dyestuff is isolated as described in Example 3. The grey-black powder so obtained dyes all kinds of leather by various methods of dyeing weakly reddish dark-blue tints of very good fastness to light and covering power. The dyestuff has the same fastness properties as the dyestuft described in Example 1.

Example 5 The diazo-suspension prepared from 173 parts of 1- aruinobenzene-4-sulfonic acid is coupled in an acid medium with 341 parts of 1-amino-8-hydroxynaphthalene-3.6- disulfonic acid (monosodiurn salt), as described in Exampie 1. The tetrazo-solution prepared from 184 parts of 4.4'-diaminodiphenyl is then poured into the mixture, and coupling is conducted in a weakly alkaline medium by adding 2000 parts by volume of a 2 N-solution of sodium hydroxide, while cooling with ice to 0 C.-5 C. After stirring for 30 minutes, the alkaline solution of 100 parts of 3.3'-dihydroxy-diphenylamine is added to the diazodisazo-compound, and the alkaline reaction mixture is stirred overnight. When the coupling is complete, the dyestufl solution is rendered acid, heated to 92 0., precipitateo' with a small quantity of sodium chloride, filtered off with suction and dried. The hexakisazo-dyestulf is obtained in the form of a grey-black powder which is readily soluble in water and has remarkably good resistance to inorganic and organic acids, alkalies and formaldehyde. It dyes all kinds of leather deep bluish black tints having a good covering power and a good fastness to light.

Example 6 A diam-suspension prepared from 22.3 parts of 1- aminonaphthalenei sulfonic acid is coupled in the usual manner in an acid medium with 34.1 parts of l-amino-S- hydroxynaphthalene-4.6-disulfonic acid. The monoazocompound so obtained is then combined in a weakly alkaline medium with a tetrazo-solution prepared from 36 parts of 4.4'-diamino-diphenylether-2.2'-disulfonic acid by adding parts of sodium carbonate. After stirring for minutes, an alkaline solution of 20.1 parts of 3.3- dihydroxy-diphenylamine is added so that the coupling takes place at a pH value of 10. When the coupling is complete, the trisazo-dyestuff so obtained is combined in an alkaline medium with a diam-suspension prepared from 17.3 parts of l-aminobenzene-4-sulfonic acid to form the tetrakisazo-dyestufi which is isolated in the usual manner, filtered off with suction and dried. The dyestutf obtained in the form of a grey-black powder has the same properties as the dyestufl described in Example 2 and dyes leather reddish black tints of very good fastness to light.

Example 7 A diaZo-solution prepared from 253 parts of l-aminobenzene-2.5-disulfonic acid is coupled in an acid medium in the usual manner with 341 parts of l-amino-8hydroxynaphthalene-3.6-disulfonic acid. When the coupling is complete, a tctrazo-solution prepared from 272 parts of 4.4-diaminodiphenyl-3.3'-dicarboxylic acid is added and 36 parts of sodium carbonate are then introduced. The weakly alkaline solution is stirred for 30 minutes. The diazo-disazo-compound so obtained is then immediately coupled in an alkaline medium with parts of 3.3-dihydroxy-diphenylamine to form the hexakisazo-dyestuif. When the coupling is complete, the dyestuif is acidified, heated to 92 C., filtered oil? with suction and dried. The grey-black powder so obtained dyes all kinds of leather by various methods of dyeing violet tints having a good covering power and the fastness properties of the dyestulf described in Example 5.

Example 8 By coupling 1 molecular proportion of the diazo-disazo-compound described in Example 1 and having the following constitution: 1-aminobenzene-4-sulfonic acid acid l amino 8 hydroxynaphthalene-3.6-disulfonic alkaline Example 9 The clarified diazo solution prepared from 17.3 parts of l-amino-2-chloro-4-nitrobenzene is coupled in an acid medium with 34.1 parts of l-'amino-8 hydroxynaphthalene-3.6-disulfonic acid and the product so obtained is then coupled in an alkaline medium with the clarified tetrazosolution prepared from 18.4 parts of 4.4' diaminodiphenyl. After stirring for 30 minutes, the diazo-disazo-compound so obtained is immediately coupled with an azo-compound prepared by combining in an alkaline medium 20.1 parts of 3.3-dihydroxy-diphenylamine with the diazosolution from 34.1 parts of l-amino-8-hydroxy-naphthalene-3.6-disulfonic acid. The resulting tetrakisazo-dyestuff is isolated as described in the foregoing examples. It dyes leather greenish dark-blue tints of good general fastness properties and very good fastness to light.

Example 10 acid amino-diphenyl 1-an1ino-8-hydroxynaphthalene- 3.6-disulfonic acid in an alkaline medium with diazotized l-aminobenzene-4-sulfonic acid and combining the intermediate-compound so obtained with 1 molecular proportion of 3.3-dihydroxy-diphenylamine. When the coupling is complete, the alkaline solution of the hexakisazodyestuff is rendered acid, heated to 92 C., salted out with a small quantity of sodium chloride, filtered-off with suction and dried. The dyestufi is obtained in the form of a grey-black powder which is readily soluble in water andhas a good resistance to inorganic and organic acids, alkalies and formaldehyde. It dyes all kinds of leather by various methods of dyeing bluish black tints of good fastness to light. The dyestutf corresponds to the following formula:

Example 11 As described in Example 10, 0.1 molecular proportion of the diazo-disazo-compound of the followingconacid stitution: l-amino-benzene-4-sulfonic acid amino 8 hydroxynaphthalene 3.6 disulfonic' acid alkaline 4.4'-diaminodiphenyl is coupled in. an alkaline medium with 0.1 molecular proportion of the trisazodyestuff of the following constitution: 1-amino-3-nitrobenzene-4-sulfonic acid l-amino-8-hydroxy-naphthaacid lene-3.6-disulfonic acid 4.4-diaminodiphenyl alkaline 3.3'-dihydroxy-diphenylamine. When the coupling is complete, the reaction product is isolated in the usual manner. The hexakisazo-dyestuif so obtained has the same good fastness properties as the dyestufi described in Example 10 and dyes leather deep blue-black tints of very good fastness to light.

Example 12 sulfonic acid 4.4'-diaminodiphenyl. The hexakisaZo-dyestuff so obtained corresponds with respect to its fastness and dyeing propertieswith the dyestuif described in Example 10.

Example 13 1 molecular proportion of the trisazo-dyestuff of the following constitution: 1-amino-2 chlorobenzene-4-sulacid ionic acid l-amino-8-hydroxynaphthalene-3.6-dialkaline sulfonic acid 4.4-diaminodiphenyl 3.3- dihydroxy-diphenylamine is coupled in an alkaline medium with 1 molecular proportion of the diazo-disazocompound of the following constitution: l-aminobenzenealkaline 4-sulfonic acid 1-amino-8-hydroxynaphthaacid lene-3.6-disulfonic acid H 4.4'-diaminodiphenyl and the dyestuif so obtained is isolated inthe usual manner. The hexakisazo-dyestutf dyes allkinds of leather by drum dyeing, brush dyeing and spray dyeing deep blue black tints of very good fastness properties.

Example 14 A hexakisazo-dyestufl is obtained by adding in-an alkaline medium to 1 molecular proportion of the diazo-disazo-compound of the following constitution: 1 aminobcnacid zene-4-sulfonic acid 1-amino-8-hydroxynaphthaalkaline I lene-3.6-disulfonic acid a 4.4diaminodiphenyl, while stirring well, 1 molecular proportion of the diazonaphthalene-3.6-disulfonic acid e- 4'.4'-diamir1 odi- 1- 7 phenyl andtthen introducing thealkaline solution' of 1 inoarvzsss 7 lecular proportion of 3.3'-dihydroxy'diphenylamine in one amine to form the tetrakisazo-dyestuif which is isolated portion. It is isolated in the usual manner and represents as described in the foregoing examples. The grey-black a grey-black powder which is readily soluble in water powder so obtained dyes leather dark-blue tints having and has the same good fastness and dyeing properties a good cove-ring power and good fastness properties. as the dyestuffs described in Examples 10 and 12. 5 The dyestuff corresponds to the following formula HzN (glH OH N=N--NH- =N HO=S son! I NH N=N l 0H -SO1H Example Example 18 0.1 molecular proportion each of the two diazo-disazo- 20 The alkaline solution of the diazo-disazo-compound compounds prepared as described in the foregoing eX- which is obtained as described in Example 1 and has arnples and having the following constitutions: the following constitution: l-aminobenzene 4 sulfonic acid acid (a) 1-aminobenzene-4-sulfonic acid l-amino-8-hyacid l-amino-S-hydroxynaphthalene 3.6 disulalkaline alkaline droxynaphthalene-3.6-d1sulfon1c acid 4-.4' ionic acid 4.4'-diaminodiphenyl, is stirred diaminodiphenyl and for minutes and then adjusted to a pH value of 4 by adding about parts by volume of a 5 N-solution of (b) lfammo'4'chlombenzene'3'sulfomc i H hydrochloric acid. After the addition of parts of 9 3 1 hydmxynaphtha'lene am 30 glacial acetic acid, a solution rendered alkaline with so- .llkalmQ 4 4' di i 3 3' di th 1dj h 1 dium hydroxide of 201 parts of 3.3 -dihydroxy-d1phenylamine and 60 parts of glacial acetic acid are added simultaneously drop by drop in the course of 2 hours. Due to the battering action of the sodium acetate which is formed, the coupling to form the tr-isazo-dyestufi takes place at a pH value of 4. When the coupling is complete, the trisazo-dyestuif is coupled in an alkaline medium with a diaZo-suspension prepared from 173 parts are poured together and, after mixing Well, combined in an alkaline medium with an alkaline solution of 0.1 molecular proportion of 3.3'-dihydroxy-diphcnylamine to 35 form the hexakisazo-dyestulf. It is isolated in the usual manner and dyes leather deep blue-black tints of good fastness properties.

E l 16 of l-aminobenzene-4-sulfonic acid to form the tetrakis- 40 ano-dyestuff which is isolated in the usual manner by The diam-suspension prepared from 173 parts of lacidifying, heating to 92 C., cooling, filtering oil with -amino-benzene-4-sulfonic acid is coupled in an acid mesuction and drying. The grey-black powder so obtained dium with 341 parts of 1-amino-8-hydroxynaphthalenedyes all kinds of leather by various methods of dyeing 3.6disulfonic acid. When the coupling is complete, the same deep black tints as the dyestulf described in the clarified tetrazo-solution of 184 parts of 4.4'-d-iamino- Example 3 having a good covering power and very good diphenyl is added to the monoazo compound, and 300 fastness to light. The dyestuff is resistant to inorganic parts of sodium carbonate are then strewn in. The weakand organic acids as well as to alkalies and formaldely alkaline reaction mixture is stirred for 30 minutes. hyde. The diazo-disazo-compound so obtained is then immedi- Example 19 ately combined in an alkaline medium with the 2120- compound obtained by wupling in an alkaline medium 0 The diazo-disazo-compound obtainable as described 201 Parts of 3 3,idihydroxydiphenylamine with diazo in Example 1 and having1 the constitution: l-aminobensuspension prepared from 23? parts of l-am1no- 2-hyzene 4 sulfonic acid l .amino s hydmxynaphma droxynaph-thalene-4- sulfonic acid. When the coupling 18 alkaline complete, the tetrakis-azo-dyestufi obtained is isolated in lene-3.6-disulfonic acid 4.4'-diaminodiphenyl the usual manner. The grey-black powder dyes all kinds is mixed, while stirring well, with a diam-suspension of leather by variou methods of dyeing deep, full darkprepared from 173 parts of l-aminobenzenel-sulfonic blue tints having a good covering power "and a very acid. Into this mixture an alkaline solution of 201 parts good fastness to light. The dyestuflf is resistant to inorof 3.3-dihydroxydiphenylamine and 100 parts by volume ganic and organic acids as well as to alkalies and form- 0 of a 10 N-solution of sodium hydroxide are introduced aldehyde. It corresponds to the following formula 6 so that .the coupling takes place in a strongly alkaline HO OH HgN on l on HO3S N=N N=N N=N N= sons HOzS SOSH Example 17 medium. When the coupling is compiete, the tetrakis- 341 Parts f g l g5.63 1. azo-dyestuif is isolated in the usual manner, filtered off fonic acid are combined in an alkaline medium with the ith ti d d i d, Th dyegtuff so Qbtained h tetrazo compound of 199 parts of 4.4'-diamino-diphenylf t 4 d d amine. When the coupling is complete, the coupling the same as Hess an yemg Propertles as the dyesmfi product is combined in an alkaline medium with an described in Example 3 and dyes kinds leather alkaline solution of 100 parts of3.3 '-dihydroxy-diphenylbluish black tints.

Constitution acid 32. 1 aminobenzene 4 sulionio acid 1 amino 8 hydroxynaphthalene 3.6 disulfonic acid e-- N (para amino benzoyl) 1.3 diaminobenzene 3 3 di hydroxy diphenylamine l aminobenzene 4 sulionic acid.

acid

33. l-aminobenzene--sulfonic acid 1-amin0- B-hydroxynaphthalene-B.ddisulfonic acid N (meta aminooenzoyl) 1.3 diaminobenzeno 3.3 dihydroxy diphenylamine 1 amino benzene 4 sulfonic acid]1 34. l-aminobenzene-l-sulfonie acid 1-amino- 8 hydroxynaphthalene 5 sulfonic acid 4.4 diamino diphenyl 3.3 dihydrcxydiphenyl amine 1 aminobenzeue 4 sulionie acid.

35. 1 amino 8 hydroxynaphthalene 4.6 disulionie alkaline acid 4.4 diamino diphenyl amine acetic acid 3.3 di hydroxy diphenylamine.

blue-black reddish dark blue.

R1-N=N H O as general formula HOaS H: HOaS-ON=N HOsS HO OH wherein R1 and R2 represent aromatic radicals selected from the group consisting of radicals of the benzene and naphthalene series, X stands for one of the group consisting of the diphenyl bond, -CH=CH,

and CONH, and Y stands for a member of the group consisting of hydrogen and the sulfonic acid group, and wherein the dyestufi molecule contains at least two snlfonic acid groups.

2. Polyazo-dyestuffs corresponding to the following general formula OH OH SOxH wherein R1 and R2 represent aromatic radicals selected from the group consisting of radicals of the benzene and naphthalene series.

3. The polyazo-dyestuff corresponding to the following formula 0 H H O on 4. The polyazo-dyestufi corresponding to the following formula SOaH References Cited in the file of this patent UNITED STATES PATENTS Krebser Apr. 22, 1941 FOREIGh PATENTS 

1. POLYAZO-DYESTUFFS CORRESPONDING TO THE FOLLOWING GENERAL FORMULA 